Field of the invention
[0001] The present invention relates to a coating formulation and to a removable coating
obtainable therefrom, and particularly a removable protective coating for ultraviolet-light
transparent parts of structures or buildings such as greenhouses, thus providing a
shading effect moderating the intensity of sun irradiation inside the building, e.g.
greenhouse. The present invention also relates to an improved cleaning agent for the
removal of such a coating, e.g. at the end of the sunny season or when the protective
effect of the coating becomes insufficient due to heavy rain or other atmospherically
difficult conditions. The present invention further relates to a method for moderating
the intensity of sun irradiation inside a building or structure such as a greenhouse
by applying such a protective coating onto an external (or an internal) surface thereof.
Background of the invention
[0002] In modern agriculture and particularly in horticulture, a lot of crops are cultivated
inside greenhouses in order to control and optimise the conditions, such as temperature,
illumination, moisture, pollination conditions, and the like, in which the plants
are grown. Glass is a common choice for a greenhouse covering because of its permanence
and durability. Plastics have also achieved a good position in agriculture and horticulture,
especially many kinds of organic glass such as acrylic can be used for covering a
greenhouse. It is also known to replace glass in greenhouses by polyethylene. Polyethylene
for greenhouse films have to be as stable as possible to the environment and in spite
of the development of synergistic light stabilisers the maximum lifetime that can
be currently achieved even in the less sunny climates is about three years. After
this time slits appear in the films from stress points, particularly where the films
are in contact with the greenhouse structure and the material has to be replaced.
In spite of this, it is increasingly more economical to use polyethylene than glass
due to the lower cost and shatter resistance of the former.
[0003] However a common problem is encountered as during the sunny season the plants grown
inside a greenhouse, whether made of glass or polyethylene, can be exposed to a large,
or even too large, amount of radiation, which can lead to perturbation, or even deterioration
of their living and growing conditions, and which often results in diminution of the
production. Such a problem is usually addressed by applying a protective coating on
the greenhouses. Such a coating comprising a pigment that will moderate the amount
of radiation that will pass into the greenhouse, and is usually used with a binder
that will make the pigment stick to the surface of the greenhouses.
[0004] Typically, the coating is applied on the surface of the greenhouse at the beginning
of the sunny season, to protect the plant inside the greenhouse from an excess of
radiation, and is removed at the end of the season, when it is neither needed nor
desired anymore.
[0005] Chalk dispersed in starch has been used for a long time, but presents a very poor
resistance to the atmospheric conditions, particularly rain, and therefore need to
be replaced several times per season.
[0006] More recently, polymeric binders have been used for the preparation of such coatings.
Different techniques have been developed in order to improve the processability, resistance
to UV radiation, or the ease of removal of the coating at the end of the season.
[0007] European Patent No.
EP-0,999,736-B1, describes a protective coating comprising a pigment and a binder being a polymer,
e.g. a vinyl polymer, having a weight-average molecular weight of 10,000-100,000 and
an acid value of 40-250. Such a coating can be removed, e.g. at the end of the sunny
season, with a removing agent comprising a strong base and a complex former. However
the coatings described in
EP-0,999,736-B1 present several drawbacks, as they usually require the use of a silane adhesion promoter,
and their removing agent comprises a strong base such as sodium hydroxide and a complex
former such, as for example, the tetrasodium salt of ethylene diamine tetraacetic
acid or the trisodium salt of nitrilo-triacetic acid. These components of the removing
agent are well known to bring environmental concerns. Additionally, the strong base
is highly corrosive and therefore brings human health risks during the removal step
which is usually performed manually. Moreover it has been observed that the protecting
coating of
EP-0,999,736-B1, when applied under certain conditions, does not suitably withstand hard atmospheric
conditions, particularly rain, during the whole annual season.
[0008] Accordingly there is still a need in the art for an improved removable coating, especially
for greenhouses, having improved characteristics, such as resistance to rain, UV-light,
atmospheric conditions in general, and allowing a single application or a reduced
number of applications of the coating by annual season while maintaining the same
level of protection against ultra-violet light. There is also a need in the art for
a protective coating, especially for greenhouses, that can easily be removed without
causing health problems to the required manpower and/or without causing environmental
problems due to its composition. For instance there is a need in the art for an improved
removing or cleaning agent that does not comprise a strong base and/or a complex former.
Summary of the invention
[0009] According to a first aspect, the present invention relates to a coating formulation
(such as a coating solution, suspension, slurry or powder) and to a removable coating
obtainable therefrom, especially for the transparent part of buildings (e.g. parts
made from glass or a transparent plastic surface) or structures such as greenhouses.
According to the broadest concept of the invention, the coating formulation and the
removable coating obtainable therefrom comprises one or more ultraviolet-light filtering
components (such as, but not limited to, pigments or colorants) and a binder system
having an average acid value from 15 to 39 and comprising at least two different acrylic-based
water-borne resins with significantly different acid value and/or water-solubility
characteristics. Preferably, said binder system may comprise a first acrylic-based
water-borne resin (a) having an acid value not above 35 and being preferably water-insoluble
at a pH above 8 and a second acrylic-based water-borne resin (b) having an acid value
from 40 to about 250, for example from 40 to about 200, from 40 to 150 or from 40
to 130. (b) is preferably water soluble at a pH above 8. The terms "
water insoluble" is used here in relation to resin (a) to indicate that when the polymer is placed
in water it appears, on visual inspection, not to dissolve. Preferably, the terms
"
water insoluble" should be construed as meaning that less than 0.05g of material can dissolve in 100
ml water and form a clear solution. The terms "
water soluble" is used here in relation to resin (b) to indicate that when the polymer is placed
in water it appears, on visual inspection, to dissolve. Whether the solution is a
true isotropic solution or has some colloidal character is not important. Preferably,
the terms "
water soluble" should be construed as meaning that at least 0.05g, preferably 0.1g of material can
dissolve in 100 ml water and form a clear solution. In an embodiment, the binder system
may comprise:
- (a) a first water-resistant acrylic-based water-borne resin having an acid value not
above 35, and
- (b) a second acrylic-based water-borne resin being water-soluble at a pH above 8.
[0010] Within this broad aspect of the invention, the protective coating can be removed
without the need for an environmentally risky strong base or the need for a (usually
expensive) complex former. For ease of application and environmental reasons, both
resins (a) and (b) are water-borne, i.e. in the form of an acrylic-based resin suspension
or emulsion in an aqueous medium such as water, at the time of applying the coating
formulation, i.e. at the time of applying the removable coating. By using acrylic-based
resin aqueous suspensions or emulsions with high solids contents, e.g. solids contents
above about 40% by weight, drying time is reduced and application is thus facilitated.
In some circumstances, it is also admissible to provide a water-dispersible acrylic-based
powder resin and to disperse it in a suitable amount of water just before preparation
of the coating formulation, i.e. just before preparation of the removable coating.
According to a specific embodiment of the present invention, the binder system may
comprise a first acrylic-based water-borne resin (a) being water-insoluble at a pH
above 8 and/or a second acrylic-based water-borne resin (b) having an acid value from
40 to about 250, for example from 40 to about 200, from 40 to 150 or from 40 to 130.
[0011] In a particular embodiment of the present invention, said binder system comprises:
- (a) a first water-resistant acrylic-based water-borne resin having an acid value not
above 35 and being water-insoluble at a pH above 8, and
- (b) a second acrylic-based water-borne resin being water-soluble at a pH above 8 and
having an acid value from 40 to about 250, for example from 40 to about 200, from
40 to 150 or from 40 to 130.
[0012] In an embodiment of the first aspect, the present invention relates to a coating
formulation or removable coating, comprising one or more light filtering components
and a binder system having an average acid value from 1 to 39, wherein said binder
system comprises:
- (a) a first water-resistant acrylic-based water-borne resin having an acid value not
above 35, and
- (b) a second acrylic-based water-borne resin being water-soluble at a pH above 8.
[0013] As an additional feature, said first water-resistant acrylic-based water-borne resin
may be water-insoluble at a pH above 8 and/or the light filtering components may be
pigments or colorants.
[0014] As an additional feature, said second acrylic-based water-borne resin (b) may have
an acid value from 40 to 250.
[0015] As an additional feature, said first resin (a) and/or said second resin (b) may be
a polymer or copolymer having one or more monomers independently selected from (e.g.
having at least one monomer selected from) the group consisting of methyl (meth)acryalte,
butyl (meth)acrylate, 2-ethylhexyl meth(acrylate), ethyl meth(acrylate), styrene,
acrylonitrile, (meth)acrylamide, vinyl acetate, vinyl chloride and (meth)acrylic acid
or alkali salts thereof.
[0016] As an additional feature, said coating may be removable with a cleaning agent comprising
a weak base (the presence of a strong base is not necessary).
[0017] In any embodiments of the first aspect, the coating formulation or coating may optionally
be free of adhesion promoter.
[0018] As an additional feature, said coating formulation or coating may further comprising
a volatile base selected from the group consisting of ammonia, mono-, di- and tri-C
1-4 alkylamines. In embodiments, the one, two or three C
1-4 alkyl groups may be independently selected from methyl, ethyl, propyl (e.g. n-propyl
or isopropyl), and butyl (e.g. n-butyl, sec-butyl, iso-butyl or tert-butyl). The use
of a volatile base is advantageous as it evaporates during the drying on the coating.
[0019] As an additional feature, said one or more light filtering components may be selected
from the group consisting of pigments and colorants.
[0020] In embodiments of the present invention, a coating formulation or coating according
to any embodiments of the first aspect of the present invention may be applied to
a transparent substrate.
[0021] The binder as defined in any embodiment of the first aspect of the present invention
is also an aspect of the present invention. In an embodiment of this aspect, the present
invention relates to a binder system for use in a coating formulation or removable
coating, said binder system comprising:
(a) a first water-resistant acrylic-based water-borne resin having an acid value of
at most 35, and
(b) a second acrylic-based water-borne resin being water-soluble at a pH above 8.
[0022] According to a second aspect, the present invention relates to a cleaning agent for
removing a removable coating according to the first aspect defined herein-above, said
cleaning agent comprising a weak base and being preferably free from a complex former
(complexing agent). Optionally the cleaning agent according to embodiment of the present
invention may further comprise a wetting agent, and/or a water-soluble thickening
agent, and/or a strong base. The terms "
water soluble" is used here in relation to the thickening agent to indicate that when the thickening
agent is placed in water it appears, on visual inspection, to dissolve. Whether the
solution is a true isotropic solution or has some colloidal character is not important.
Preferably, the terms "
water soluble" as used here in relation with the thickening agent should be construed as meaning
that at least 0.05g of material, preferably 0.1g of material can be dissolved in 100
ml water and form a clear solution. According to yet another aspect, the present invention
relates to a process for moderating the effects of ultraviolet light (e.g. from the
sun) irradiation inside a building or structure (such as, but not limited to, a greenhouse),
said process comprising a step of applying a coating formulation, i.e. applying a
removable coating according to the first aspect of the invention onto an external
(or internal) ultraviolet light transparent surface of said building or structure,
e.g. said greenhouse. The said transparent surface may be made of mineral glass or
organic glass such as for instance a transparent rigid and shock-resistant organic
polymers (e.g. polycarbonate or acrylic (Polymethyl methacrylate (PMMA))). Although
its transparency level and mechanical properties may be lower, the greenhouse surface
may also be made of a polyethylene foil.
[0023] In an embodiment of the second aspect, the present invention relates to a cleaning
agent for removing a coating according to any embodiments of the first aspect of the
present invention, comprising a weak base.
[0024] As an additional feature of this second aspect, said weak base may exhibit an acid
dissociation constant value of the corresponding conjugated acid smaller than 13.
[0025] In any embodiments of the second aspect of the present invention, the cleaning agent
may be free of a complex former.
[0026] As an additional feature, the cleaning agent may further comprise a strong base i.e.
having a pKa of at least 13.
[0027] As an additional feature, said cleaning agent may be in the form of an aqueous solution
have a pH between 8 and 11.
[0028] In any embodiments of the second aspect of the present invention, the cleaning agent
may be free of organic solvents.
[0029] In a further aspect, the present invention relates to a process for moderating the
effects of ultra-violet irradiation inside a building having an ultraviolet-light
transparent surface, said process comprising a step of applying a coating formulation
or coating according to any embodiment of the first aspect onto said ultraviolet-light
transparent surface.
[0030] In yet a further aspect, the present invention relates to a method for applying a
coating formulation or coating, wherein a coating formulation or coating according
to any embodiment of the first aspect is applied to a substantially ultraviolet-light
transparent surface, and wherein said coating formulation forms an ultra-violet light
protective layer after drying.
[0031] In still a further aspect, the present invention relates to a kit comprising a coating
formulation according to any embodiment of the first aspect of the present invention
and a cleaning agent according to any embodiments of the second aspect of the present
invention.
[0032] In still a further aspect, the present invention relates to a greenhouse (or to any
other UV-transparent surface) provided with a coating according to any embodiments
of the first aspect of the present invention on its outer (or inner) surface.
[0033] Another aspect of the present invention relates to the use of a weak base for removing
a removable protective coating for ultraviolet-light transparent parts of structures
or buildings such as greenhouses.
Detailed description of the invention
[0034] The present invention will be described with respect to particular embodiments but
the invention is not limited thereto but only by the claims. Where the term " comprising
" is used in the present description and claims, it does not exclude the presence
of other elements or steps. Where an indefinite or definite article is used when referring
to a singular noun e.g. " a " or " an ", " the ", this includes a plural of that noun
unless something else is specifically stated.
[0035] The term " comprising ", used in the claims, should not be interpreted as being restricted
to the means listed thereafter; it does not exclude other elements or steps. Thus,
the scope of an expression such as " a device comprising means A and B " should not
be limited to devices consisting only of components A and B. It means that with respect
to the present invention, the only functionally relevant components of the device
are A and B.
[0036] Furthermore, the terms first, second, third and the like in the description and in
the claims, are used for distinguishing between similar elements and not necessarily
for describing a sequential or chronological order. It is to be understood that the
terms so used are interchangeable under appropriate circumstances and that the embodiments
of the invention described herein are capable of operation in other sequences than
described or illustrated herein.
[0037] As used herein and unless provided otherwise, the terms "
ultraviolet-light transparent" means transparent to at least part of the UV spectrum. More in particular, it means
transparent to at least part of solar UV, i.e. to at least part of UVA.
[0038] As used herein and unless provided otherwise, the terms "
water-resistant" means "which does not degrade in contact with water having a pH of 7 or under".
[0039] As used herein and unless provided otherwise, the terms "alkali salt" is construed
as being synonym of "alkaline salt" and refers to salts of Na, K, Li, Rb, or Cs as
well as to alkaline earth salts such as salts of Be, Mg, Ca, Sr or Ba.
[0040] According to a first aspect, the present invention provides a coating formulation
and a removable coating obtainable therefrom. The removable coating may be a removable
coating for buildings or structures having transparent parts, e.g. mineral glass or
organic polymers (e.g. polycarbonate or acrylic or polyethylene) windows such as greenhouses.
The coating formulation or removable coating according to this aspect of the invention
can be applied to an ultraviolet light (e.g. solar UV) transparent surface of such
buildings or structures having transparent parts, e.g. a greenhouse. This may occur
at the beginning of the sunny season and the coating preferably provides a shading
effect, i.e. it moderates the intensity of the visible light and moderates the intensity
of the ultraviolet light (e.g. sun) radiation that enters the building or structure
such as a greenhouse.
[0041] Surprisingly, it has been found that the coating according to this aspect of the
present invention shows good adhesive property to both polymer and glass surface as
well as strong resistance to atmospheric conditions, e.g. rain and/or wind, for a
long period of time, e.g. during the whole sunny season, while still being removable
in an efficient way using a weak base solution and without the need for the environmentally
hazardous complex forming agent (i.e. complexing agent) required according to the
prior art.
[0042] The kind of light reflecting and/or filtering component(s) or colorant(s) or pigment(s)
that can be used in a coating formulation or coating according to this aspect of the
invention is not a limiting feature of the present invention. Any light filtering
component or pigment or colorant or combination of pigments, light filtering components
or colorants known in the art, which can be suitably dispersed into the binder system
and provide the desired protective action and/or covering power, can be used. The
skilled person will be able to adapt the type and quantity of the light filtering
component(s) or colorant(s) (e.g. pigment(s) or dye(s)) to be used according to the
properties that are desired for the protective coating. Pigments are usually preferred
as their life-time under solar radiation is longer than for dyes. For example the
colorant (e.g. pigment) may be present in an amount ranging from about 30 to about
95% by weight, preferably 40 to 85% by weight, of the removable coating formulation.
On a dry weight basis, the colorant (e.g. pigment(s)) may be present for instance
in an amount ranging from about 65% to about 95%, preferably from about 70% to about
90%, more preferably from about 75% to about 90%. Suitable pigments include for example,
but are not limited to, calcium carbonate, titanium oxide, aluminium silicate, magnesium
silicate, gypsum, baryte, and combinations thereof.
[0043] The binder system to be used according to the first aspect of the present invention
is an important parameter of the invention. It is preferably present in an amount
ranging from about 5 to about 60% by weight of the removable coating formulation.
On a dry weight basis, the binder is preferably present in an amount ranging from
about 5 to about 60%, preferably from about 5 to about 40% by weight, more preferably
from about 10 to about 30% by weight, even more preferably form about 10 to about
25% by weight and most preferably from about 11 % by weight to about 22% by weight.
The binder system according to this aspect of the present invention comprises a mixture
of two or more different acrylic-based resins, and by suitably balancing the respective
proportions of these two or more resins in the binder system while maintaining an
average acid value from 15 to 39 surprisingly provides a desirable compromise between
water-resistance of the removable coating during protective use, and ease of removal
of the coating after protective use, especially the ability to remove the protective
coating without the need for an environmentally risky strong base or the need for
a complex former, e.g. by using the removing solution, according to embodiments of
the present invention.
[0044] According to a specific embodiment of the present invention, the first acrylic-based
resin (a) is preferably present in an amount ranging from 30 to 95% (e.g. 30 to 70%
or 40 to 60%) by weight, preferably 50 to 90%, more preferably 55 to 90%, most preferably
from 57 to 88% of said binder system and the second acrylic-based resin (b) is preferably
present in an amount ranging from 70 to 5% (e.g. 70 to 30% or 60 to 40%), preferably
50 to 10%, more preferably 45 to 10%, most preferably 43 to 12% by weight of said
binder system.
[0045] The type of acrylic-based resin to be used in the binder system of the present invention
can be adapted over a broad range of commercially available or easily accessible products
such as polymers and copolymers comprising one or more monomers such as, but not limited
to, methyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl meth(acrylate), ethyl
meth(acrylate), styrene, α-methylstyrene, (meth)acrylonitrile, (meth)acrylamide, (meth)acrylic
acid, vinyl acetate, vinyl chloride and alkaline salts thereof. The term " acrylic-based
" as used herein refers to a resin wherein the acrylic or methacrylic monomer(s) are
predominant by weight with respect to the whole resin composition but does not exclude
the presence of minor amounts of non-acrylic comonomers (e.g. styrene and the like)
compatible therewith.
[0046] According to another specific embodiment of the present invention, the second acrylic-based
resin (b) may comprise :
- from 40 to 70 wt-% of methyl methacrylate,
- from 20 to 40 wt-%, of butyl acrylate, and
- from 7 to 20 wt-%, of (meth)acrylic acid.
[0047] Some acrylic-based resins suitable for use as the second (preferably higher acid
value) acrylic-based resin (b) of the coating formulation or coating according to
the first aspect of this invention are commercially available, such as for example,
but not limited to, resins available under the trade names NeoCryl B817 and NeoCryl
BT26 (both from DSM Resins, Waalwijk, The Netherlands) and Craymul 2701 (from Cray
Valley SA, France).
[0048] According to another specific embodiment of the present invention, the first acrylic-based
resin (a) may comprise :
- from 10 to 80 wt-% of methyl methacrylate and/or methyl acrylate,
- from 0 to 25 wt-% of styrene,
- from 0 to 60 wt-% of butyl acrylate, and
- less than 7 wt-%, e.g. from 0 to 5 wt-% of (meth)acrylic acid.
[0049] Some acrylic-based resins suitable for use as the first (preferably lower acid value)
acrylic-based resin (a) of the coating formulation or coating according to the first
aspect of this invention are commercially available, such as for example, but not
limited to, a resin available under the trade name NeoCryl FL711 (from DSM Resins,
Waalwijk, The Netherlands) or can be manufactured using methods well known in the
art.
[0050] The coating formulation or removable coating of the present invention are easily
produced by simply mixing, in one or more steps, its essential components, i.e. the
first (preferably lower acid value) acrylic-based water-borne resin (a), the second
(preferably higher acid value) acrylic-based water-borne resin (b), and the one or
more light filtering agents in suitable proportions until a homogeneous mixture including
a binder system with the desired average acid value is obtained.
[0051] According to a specific embodiment the protective coating of this invention is easily
removable with a cleaning agent comprising a weak base and/or being free of any complexing
agent.
[0052] In addition to the light filtering component(s), colorant(s) or pigment(s) and the
binder system herein above described, the coating liquid or removable coating according
to this aspect of the invention can optionally further comprise additives known in
the art, such as one or more biocides, wetting agents, defoamers, thickeners, light
stabilizers, and the like.
[0053] According to a specific embodiment, the coating liquid or removable coating of this
invention is free of any adhesion promoter (i.e. adhesion promoting additives) such
as a silane.
[0054] According to a specific embodiment, the coating formulation of this invention can
be manufactured in a ready-to-apply form, e.g. further comprising water and a volatile
base, and can optionally be diluted at will in order to realise the desired shading
of the coating. The coating formulation according to embodiments of the present invention
can also be in the form of a high solid content formulation requiring further dilution
before application. In coating formulation according to embodiments of the present
invention, the volatile base may be selected from the group consisting of ammonia,
mono-, di- and tri-C
1-4 alkylamines, and mixtures thereof. In embodiments, the one, two or three C
1-4 alkyl groups of the alkylamine may be independently selected from methyl, ethyl,
propyl (e.g. n-propy or isopropyl), and butyl (e.g. n-butyl, sec-butyl, iso-butyl
or tert-butyl).
[0055] In principle, but without being bound by any theory, the presence of the volatile
base is useful in making the binder system soluble, dispersible (leading to a stable
dispersion) or suspendible (leading to a stable suspension) in water, therefore allowing
an easy application of the coating, e.g. on the surface of glass e.g. in a greenhouse,
preferably by spraying the solution, using for example a paint spray gun, a garden
sprayer or the like. After about 30 minutes, or a few hours, the volatile base spontaneously
evaporates into the atmosphere, and the binder system solidifies, thus providing a
protective coating with adequate adhesive strength and resistance to atmospheric conditions,
e.g. rain and/or wind, especially on a glass surface.
[0056] According to a second aspect, the present invention provides an improved cleaning
agent which is able to remove the protective coating of the first aspect of the invention.
This cleaning agent comprises a weak base, and optionally a wetting agent and/or a
water-soluble thickening agent.
[0057] In a third aspect, the present invention relates to the use of a cleaning agent according
to any embodiments of the second aspect of the present invention for removing a removable
coating according to any embodiments of the first aspect of the present invention.
In other words, in embodiments of the third aspect, this invention provides the new
use of a weak base for removing the removable coating herein-above defined within
a first aspect. The weak base suitable for the cleaning agent according to this aspect
of the invention is preferably soluble in water. As used in relation with the weak
base, the terms "
soluble in water" mean that when the weak base is placed in water it appears, on visual inspection,
to dissolve and to form a clear solution. Preferably, the terms "soluble in
water" as used in relation to a weak base should be construed as meaning that at least
0.05g of material, preferably 0.1g of material, can be dissolved in water and form
a clear solution.
[0058] According to a specific embodiment of the invention, the weak base preferably exhibits
an acid dissociation constant (pKa) value of the corresponding conjugated acid smaller
than 13, such as, but not limited to, sodium carbonate, potassium carbonate, ammonium
carbonate and the like. Preferably, the pKa of the conjugated acid of the weak base
in at least 10.
[0059] According to another specific embodiment, the cleaning agent of this invention is
free of any complex forming (or complexing) agent. According to embodiments, the cleaning
agent may optionally further comprise a strong base. Such a strong base should be
compatible with the weak base under the conditions of use, i.e. in the presence of
the coating to be removed. Exemplary strong bases include, but are not limited to,
alkaline hydroxides such as potassium hydroxide or sodium hydroxide.
[0060] The cleaning agent according to the second aspect of the present invention can take
the form of (i) a dry composition (i.e. comprising no or a small amount of water such
as e.g. 10% or less, 5% or less or 1% or less), of (ii) a concentrated aqueous solution
to be diluted before use (e.g. to obtain a diluted solution having a pH preferably
between 8 and 11 or more preferably between 9 and 10), or of (iii) a diluted, ready
to use aqueous solution (e.g. having a pH preferably between 8 and 11 or more preferably
between 9 and 10). Diluted ready to use solutions can of course be further diluted
(e.g. as long as the pH of the further diluted solution remains at or above 8). This
is for instance the case with ready to use formulations 4-8 of table 3 which can be
further diluted up to a factor 10, preferably up to a factor 7, e.g. by a factor 3
to 7 or by a factor 5 to 7 before use. Although they are usable undiluted, a dilution
improves the fluidity and applicability of those formulations.
[0061] According to a specific embodiment, the cleaning agent of this invention is in the
form of an aqueous solution having a pH preferably between 8 and 11, more preferably
between 9 and 10. To this effect, the cleaning agent, in a ready use form, preferably
has a pH of from 8 to 11, preferably 9 to 10. Of course cleaning formulation having
a higher pH remains within the scope of the present invention as a simple dilution
would bring them in the preferred pH range. As understood by the person skilled in
the art, the exact nature of the weak base, its molecular mass, its strength (i.e.
the pKa of its conjugated acid) combined with the pH to be obtained in the cleaning
agent's solution, are determining factors for the amount of the weak base to be used.
For example an amount varying from 0.3 to 7%, preferably 0.5 to 5% by weight of the
cleaning agent, is suitable for a weak base such as sodium carbonate (having a molecular
mass about 106 g/mole, and a pKa of the conjugated acid of about 10.3). In its dry
form, the cleaning agent of the present invention can for instance comprise between
10 and 85%wt of weak base.
[0062] The kind and amount of water-soluble or hydrophylic thickener to be used according
to this second aspect of the invention are not limiting features and a large variety
of water-soluble thickener known in the art and providing the suitable effect, i.e.
increasing the viscosity of the cleaning agent therefore preventing it from flowing
off the treated surface too rapidly, can be used, such as for example: polyvinyl alcohol,
hydroxyethyl cellulose, crosslinked acrylic copolymers and the like and mixtures thereof.
The amount of water-soluble thickener usually ranges from 0 to about 5% by weight
of the ready to use cleaning agent according to embodiments of the present invention
but it can be up to 12%wt in the case of crosslinked acrylic copolymer. In its dry
form (calculated for 0% of water), the cleaning agent of the present invention can
for instance comprise between 12 and 80%wt of thickener.
[0063] The kind and amount of wetting agent to be used according to this second aspect of
the invention are not limiting features and a large variety of wetting agents known
in the art and providing the suitable effect, i.e. facilitating the impregnation of
the coating, can be used according to this invention, such as for example, sodium
lauryl sulfate, or similar product. Some suitable wetting agent are commercially available,
such as for example but not limited to Empicol 0045 (Huntsman, Holland), Disponil
SDS G (Cognis, Germany). The wetting agent can for instance be used between 0 and
0.75% by weight of the ready to use cleaning agent. In its dry form (calculated for
0% of water), the cleaning agent of the present invention can for instance comprise
between 0 and 15%wt of wetting agent.
[0064] In a preferred embodiment, the cleaning agent comprises (in its ready to use form):
- from 80 to 88%wt of water,
- from 8 to 12%wt of thickener comprising at least a crosslinked acrylic copolymer thickener
(such as e.g. Primal ASE60),
- from 0 to 0.5%wt of wetting agent (such as e.g. Empicol 0045), and
- from 3 to 7%wt of a weak carbonate base such as e.g. sodium carbonate.
[0065] The cleaning agent of this last preferred embodiment can still be diluted up to 7
times or even 10 times, e.g. between 5 to 7 times before use. This last dilution can
for instance be performed directly before use. Examples of cleaning agents according
to this preferred embodiment are shown in column 7-8 of table 3. In another preferred
embodiment, the cleaning agent comprises (in its dry form (calculated for 0% of water)):
- from 60 to 70%wt of thickener comprising at least a crosslinked acrylic copolymer
thickener (such as e.g. Primal ASE60),
- from 1 to 2%wt of wetting agent (such as e.g. Empicol 0045), and
- from 25 to 40%wt, preferably from 30 to 35%wt of a weak carbonate base such as sodium
carbonate. Examples of cleaning agents according to this preferred embodiment are
shown in column 7-8 of table 4.
[0066] According to a specific embodiment, the cleaning agent of this invention may preferably
be substantially free of any organic solvent. For instance it may comprise from 0
to 2%wt of organic solvent, preferably 0 to 1%wt, most preferably from 0 to 0.1% or
organic solvent.
[0067] To remove the removable coating according to the first aspect the cleaning agent
according to the second aspect of the invention is suitably applied, for example by
pouring or by spraying (e.g. with a garden sprayer or a paint spray gun) in order
to impregnate the coating, preferably in a humid atmosphere. The contact time before
washing can be varied over a broad range, e.g. between 30 minutes and 24 hours, after
which the surface (e.g. greenhouse) is washed with water either by spraying or pouring
water, or even by (natural) rain. Since the cleaning agent according to the second
aspect of the invention usually has low volatility, it may still be effective after
24 hours in the presence of water, e.g. rain.
[0068] According to a specific embodiment, the cleaning agent is provided in a concentrated
form suitable for dilution (e.g. 5 to 10 times) before, preferably just before, use,
i.e. before removal of the coating.
[0069] According to another aspect of the present invention, the coating extensively described
in the first aspect herein-above may also be removed, when applied to a rigid and
scratch-resistant surface such as a glass greenhouse, by mechanical means such as
a rotating brush of an automatic or semi-automatic brushing or cleaning system operated
in the presence of water. Suitable examples of such systems include, but are not limited
to, the Roofmaster roofcleaners commercially available from Besseling & All Techniek,
Heerhugowaard, The Netherlands. According to another aspect, the present invention
provides a process for moderating the sun irradiation inside a building or structure
having transparent parts such as a greenhouse, comprising the step of applying a coating
according to the first aspect of the invention onto a substantially transparent surface,
preferably the outer wall surface, of the building or structure, e.g. a greenhouse.
According to yet another aspect, the present invention provides a method for applying
a coating, wherein a coating according to the above specifications is applied to a
substantially transparent surface, which said coating forms an ultra-violet light
protective layer after drying. Although the drying time of said coating may depend
upon parameters such as the solids contents of the resins present in the coating,
the amount of coating applied per surface unit of the substantially transparent surface,
the temperature of application and the like, one advantage of the coating of this
invention is a short drying time, e.g. not more than about 60 minutes at a temperature
ranging from about 20 to 25°C, and no more than about 20 minutes at higher temperatures.
According to this invention, the substantially transparent surface may be an outer
wall surface of a greenhouse. The greenhouse may be made of glass, organic glass (i.e.
organic glass-like polymers) such as but not limited to acrylic or polycarbonate,
or polyethylene. In order to sustain the ultra-violet irradiation regime of certain
sunny climates, linear low density polyethylene (LLDPE) and low density polyethylene
(LDPE) films may contain a high molecular weight hindered amine light stabiliser (HALS)
only, or optionally along with a primary antioxidant (i.e. Irganox 1010) and a secondary
antioxidant (i.e. Irgafos 168 or Alkanox TNPP), and/or an ultra-violet additive (i.e.
Chimassorb 81 or Tinuvin P or Tinuvin 326).
[0070] According to yet another aspect, the present invention provides a kit comprising
a coating formulation and a cleaning agent, both being as specified herein-above in
any of the first and second embodiment of the present invention respectively.
[0071] The invention will be further described through non-limiting examples of coating
composition and cleaning agent compositions.
Ingredients used in the Examples:
[0072] Neocryl B817 refers to a commercially available (from DSM Neo Resins, The Netherlands)
resin having an acid value of 60, having a solid content of 100% by weight and having
a monomeric composition of about 60 weight-% of methyl methacrylate, about 30 weight-%
of butyl acrylate and about 10 weight-% of acrylic acid. Acticide MBF50 refers to
a commercially available biocide from THOR. BYK024 refers to a commercially available
de-foamer from BYK Chemie. BYK154 refers to a commercially available wetting agent
from BYK Chemie.
[0073] CaCO
3 refers to commercially available (from Omya) calcium carbonate used as filler and
pigment.
[0074] Deuteron XG is a commercially available thickener from Deuteron.
[0075] Neocryl FL711 refers to a commercially available (from DSM Neo Resins, The Netherlands)
resin having an acid value of about 25, having a solid content of 20% by weight and
having a monomeric composition of about 15 weight-% of methyl methacrylate, about
15 weight-% of styrene, about 65 weight-% of methyl acrylate and about 5 weight-%
of (meth)acrylic acid.
[0076] Craymul 2701 refers to a commercially available (from Cray Valley, France) resin
having an acid value of 130.
[0077] 2AQ076 is a copolymer resin having an acid value of less than 10, having a solid
content of about 50% by weight and having a monomer composition of 50-55 weight-%
of methyl methacrylate, 40-45 weight-% of butyl acrylate and about 1.50 weight-% methacrylic
acid.
[0078] Polyvinyl alcohol refers to a commercially available polyvinyl alcohol of grade BP-20
from Omya Peralta GmbH.
[0079] Hydroxyethylcellulose refers to a commercially available hydroxyethylcellulose (Tylose
H30000YP2) from SE Tylose GmbH.
[0080] Empicol 0045 refers to a wetting agent (lauryl soduim sulfate) commercially available
from Huntsman.
[0081] Sodium carbonate refers to commercially available sodium carbonate from Solvay, Brunner
Mond.
[0082] Potassium carbonate refers to commercially available potassium carbonate from Société
des Produits Chimiques d'Harbonnières.
[0083] Ammonium carbonate refers to commercially available ammonium carbonate from B.A.S.F
(Ludwigshafen, Germany).
[0084] Primal ASE60 refers to a commercially available crosslinked acrylic copolymer thickener
from Rohm and Haas.
Example 1 - Preparation of the removable coating in a higher solid content.
[0085] In a reaction vessel the following formulations (see table 1) were made by adding
and mixing the ingredients in the following proportions by weight.
Table 1
Ingredients |
Formulation 1 |
Formulation 2 |
Formulation 3 |
Formulation 4 |
Water |
53.29 |
110.4 |
96.06 |
110.4 |
Ammonia |
3.81 |
6.5 |
5.7 |
6.5 |
Neocryl B817 |
19.03 |
39 |
34 |
0 |
Craymul 2701 |
0 |
0 |
0 |
36.0 |
Water |
49.17 |
142.85 |
124.8 |
103.8 |
Acticide MBF50 |
4.76 |
3.9 |
2.3 |
3.9 |
BYK024 |
1.59 |
2.6 |
2.3 |
2.6 |
BYK154 |
1.59 |
1.3 |
1.1 |
1.3 |
CaCO3 |
634.41 |
519.5 |
582 |
519.5 |
Water |
88.27 |
120.2 |
104.9 |
120.2 |
Deuteron XG |
1.34 |
1.83 |
1.6 |
1.83 |
Neocryl FL711 |
142.74 |
0 |
0 |
0 |
2AQ076 |
0 |
51.95 |
45.2 |
94 |
Example 2 - application of the coatings.
[0086] The compositions of example 1 were diluted with water in a ratio from 1/2 to 1/5,
in order to provide different shading effects. The resulting aqueous solutions were
applied by spraying with a garden sprayer. Applications were performed on a glass
plate at an angle of 45°. After 30 minutes at room temperature (20-25°C), the coatings
became rain-resistant.
[0087] The dry film thickness and corresponding shading effect (light attenuation) obtained
for the formulations of table 1 are represented in table 2. All formulations gave
similar film thickness and light attenuation.
Table 2
Dilution Ratio (coating/water) |
Dry film thickness (µm) |
Light attenuation |
1/2 |
7-9 |
35-40 % |
1/3 |
4 |
25-30 % |
1/4 |
3-4 |
20-25 % |
1/5 |
2 |
15-20 % |
[0088] The dry film thickness was measured with a thickness gauge (e.g. according to ASTM
4138).
[0089] The Light attenuation value indicated in table 2 was calculated by the ratio daylight
exposure / light attenuation measured through the coated panel. The measurements were
realised with a Lux-meter, type " Testo 545 ".
[0090] The coatings were considered as rain resistant when spraying water on the coating
with a garden sprayer for 30 seconds does not affect the coating and is remain undamaged.
Example 3 - preparation of the cleaning agent.
[0091] In a reaction vessel, formulations (see table 3) were made by adding and mixing the
ingredients in the following proportions by weight.
Table 3
Formulation |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
Water |
59.5 |
59.5 |
59.5 |
94 |
83.5 |
83 |
59.6 |
60.1 |
Primal ASE60 |
- |
- |
- |
- |
- |
- |
10 |
10 |
Polyvinyl alcohol |
3 |
3 |
3 |
- |
- |
- |
- |
- |
Hydroxy- ethylcellulose |
- |
- |
- |
1 |
1 |
1.5 |
0.5 |
- |
Water |
27 |
27 |
27 |
- |
- |
- |
4.65 |
4.65 |
Empicol 0045 |
0.5 |
0.5 |
0.5 |
- |
0.5 |
0.5 |
0.25 |
0.25 |
Water |
9.5 |
9.5 |
9.5 |
- |
10 |
10 |
20 |
20 |
Sodium carbonate |
0.5 |
- |
- |
5 |
5 |
5 |
5 |
5 |
Potassium Carbonate |
- |
0.5 |
- |
- |
- |
- |
- |
- |
Ammonium Carbonate |
- |
- |
0.5 |
- |
- |
- |
- |
- |
Total |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
[0092] The cleaning agents of table 3 comprising 5 %wt of sodium carbonate can be diluted
up to 7 times or event 10 times before use, preferably 3 to 7 times, most preferably
5 to 7 times before use.
[0093] Table 4 shows the same formulations as presented in table 3 but on a dry weight basis
(calculated without taking water into consideration).
Table 4
Formulation |
1 |
2 |
3 |
4 |
5 |
6 |
7 |
8 |
Primal ASE60 |
- |
- |
- |
- |
- |
- |
63.5 |
65.6 |
Polyvinyl alcohol |
75 |
75 |
75 |
- |
- |
- |
- |
- |
Hydroxy-ethylcellulose |
- |
- |
- |
16.7 |
15.3 |
21.4 |
3.2 |
- |
Empicol 0045 |
12.5 |
12.5 |
12.5 |
- |
7.7 |
7.2 |
1.6 |
1.6 |
Sodium carbonate |
12.5 |
- |
- |
83.3 |
77 |
71.4 |
31.7 |
32.8 |
Potassium Carbonate |
- |
12.5 |
- |
- |
- |
- |
- |
- |
Ammonium Carbonate |
- |
- |
12.5 |
- |
- |
- |
- |
- |
Total |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
100 |
Example 4 - Removal of the coatings
[0094] In order to reproduce the natural conditions, the coatings of example 2 were subjected
to an accelerated ageing by storing them in an oven at 70°C for one or two weeks.
Tests on naturally aged panels were also realised.
[0095] The panels thus prepared where washed according to one of the two following procedures.
[0096] Procedure 1: the cleaning solutions were sprayed onto the panels using a garden sprayer,
in order to impregnate the coatings. After 30 minutes, the panels were washed by spraying
water.
[0097] Procedure 2: the cleaning solutions were sprayed onto the panels using a garden sprayer,
in order to impregnate the coatings. After 24 hours the panels were exposed to natural
rain.
[0098] After these washing procedures, the coatings were totally removed. In some cases,
a slight haze was present directly after cleaning, but was easily removed by rain
in the few days after cleaning.